The double-filled skutterudites Cey/2Yby/2Fe4-xCoxSb12 and Cey/2Yby/2Fe4-xNixSb12 have been synthesized as single phase materials. The evolution of the lattice parameters and of the filling fractions with substitutions on the transition metal site have been studied by X-ray diffraction and electron probe microanalysis, respectively. Both results were compared to that of single filled series (Ce/Yb)(y)Fe4-x(Co/Ni)(x)Sb-12. It shows that double-filled skutterudites can be understood as a solid solution between single filled ones. The valence states of Ce and Yb in all series have been studied using X-ray absorption spectroscopy at the L-3 edges, and we discuss their relationships with structural parameters. Ce is always trivalent, whereas Yb valence state decreases as Yb fraction increases. No distortion of the environment or sub-position of Yb in the cage have been seen by neutron diffraction. The Seebeck coefficient has been measured using a home made apparatus from 120 K to 300 K. It shows a crossover from p- to n-type conductivity for Co or Ni rich skutterudites in the six series. We discuss the influence on the room temperature thermopower of valence states, filling fractions and substitution rate on the transition metal site. Thermopower seems to be only driven by charge carriers concentration. (c) 2004 Elsevier Ltd. All rights reserved.